JP3848742B2 - UV shielding pigment - Google Patents

UV shielding pigment Download PDF

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JP3848742B2
JP3848742B2 JP19202197A JP19202197A JP3848742B2 JP 3848742 B2 JP3848742 B2 JP 3848742B2 JP 19202197 A JP19202197 A JP 19202197A JP 19202197 A JP19202197 A JP 19202197A JP 3848742 B2 JP3848742 B2 JP 3848742B2
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zinc oxide
pigment
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JPH1121468A (en
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民生 野口
幸隆 渡辺
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メルク株式会社
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Priority to EP98111383A priority patent/EP0889099B1/en
Priority to ES98111383T priority patent/ES2207769T3/en
Priority to DE69818556T priority patent/DE69818556T2/en
Priority to TW087110588A priority patent/TW513471B/en
Priority to KR1019980026581A priority patent/KR100538606B1/en
Priority to US09/109,085 priority patent/US6086666A/en
Priority to CN98115573A priority patent/CN1125150C/en
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Description

【０００１】
【産業上の利用分野】
本発明は、紫外線遮蔽用顔料、詳しくは、薄片状粉末表面に酸化亜鉛粒子及び硫酸バリウム粒子を被覆せしめた特にＵＶ−Ａを遮蔽する紫外線遮蔽用顔料、その製造方法及びその使用に関する。
【０００２】
【背景技術】
紫外線領域の中で波長２９０〜４００ｎｍの地上での光量は太陽光線中の約６％を占め、その中で短波長側の２９０〜３２０ｎｍ領域（以下、ＵＶ−Ｂと記す）が約０．５％、長波長側の３２０〜４００ｎｍ（以下、ＵＶ−Ａと記す）が約５．５％で、ＵＶ−Ａの光量が多い。このＵＶ−Ａは、波長が長いため、短波長の紫外線と比べて雲や、窓ガラスを透過し易く、日常生活において皮膚の被爆量が多くなり、さらに皮膚組織の深部にまで到達する。ＵＶ−Ｂは、表皮で散乱ないし、吸収されて、皮膚にサンバーン等の炎症を起こすのに対し、ＵＶ−Ａは、皮下の真皮にまで浸透し、皮膚組織内部でラジカルが発生し、皺、弛み、弾力性の低下など光加齢の原因となり、細胞膜や遺伝子に悪影響を与えるといわれている。従って、紫外線を防ぐためには、単に紫外線全領域を遮蔽するということだけでなく、特に、このＵＶ−Ａを遮蔽することが重要となり、その関心が高まってきている（粧技誌 ３１ Ｎｏ．１ ｐ．１４〜３０ １９９７）。
【０００３】
この紫外線遮蔽効果を有する素材としては、微粒子酸化チタン（例えば、特公昭４７−４２５０２号公報）、微粒子酸化鉄（例えば、特開平５−２７９２３５号公報）、微粒子酸化亜鉛（例えば、特開昭６０−２３１６０７号公報）、及び微粒子酸化セリウム（例えば、特開平２−８２３３１２号公報）などの金属酸化物、ベンゾトリアゾール系の有機系紫外線吸収剤等が知られ、市販されている。しかし、これらの市販されている紫外線遮蔽剤あるいは吸収剤は、紫外線の遮蔽効果が充分でなかったり、あるいは使用目的が限られるなど、次のような改善すべき問題点を有している。
【０００４】
例えば、微粒子酸化チタンは、ＵＶ−Ａの吸収が小さく、ＵＶ−Ａ領域の光散乱による遮蔽効果を発揮せしめるためには、その粒子径を大きくしなければならず、その為に粒子自体の透明性が失われ白色度が増し、結果として、その用途が制限されることになる。微粒子酸化鉄は、他の金属酸化物に比べて紫外線遮蔽効果が劣っており、またそれ自体、褐色を有しているため用途が制限されることになる。微粒子酸化亜鉛は、優れた紫外線遮蔽効果を有しているが、凝集性が強く、最適の紫外線遮蔽効果が得られる粒子径の一次粒子に分散させるためには強い攪拌力を有する特殊な分散装置を使用する必要があり、一旦、一次粒子を分散することができても、容易に再凝集してしまうという使用上の問題を有している。
【０００５】
また、微粒子酸化セリウムは、極めて高価であるため、特殊目的のほかはほとんど実用性はないといってよい。
他方、ベンゾトリアゾール系などの有機紫外線吸収剤は、紫外線の吸収性に優れているものの、有機化合物であるところから基本的に安定性に欠けており、効果の持続性は期待できない。また、有機系紫外線吸収剤の化粧料用添加剤としての使用は安全性の点から大変厳しい条件が課せられ、制限される。
【０００６】
本発明者らは、上記のような実情に鑑み、紫外線遮蔽用顔料の開発研究を鋭意進めた結果、薄片状粉末に酸化亜鉛粒子と硫酸バリウム粒子とを被覆することによって、高い紫外線遮蔽効果、特にＵＶ−Ａを遮蔽し、かつ酸化亜鉛の凝集性が改善されることを見出し、また、化粧料に添加した場合、その基本的特性である伸展性、付着性に優れた紫外線遮蔽用顔料を開発することに成功した。本発明は、かかる知見に基づくものである。
【０００７】
【発明の開示】
本発明は、薄片状粉末表面に平均粒子径０．１〜２．０μの硫酸バリウム粒子および長径の平均径が０．０５〜１．５μの酸化亜鉛針状晶粒子を被覆せしめたことを特徴とする紫外線遮蔽用顔料を提供するものである。
【０００８】
また、本発明は、薄片状粉末を水に懸濁させ、この懸濁液に
（ａ）水溶性バリウム化合物、及び
（ｂ）（ａ）のバリウムイオンの当量比より多い硫酸イオンを含む溶液、を用いて、
予め（ａ）を所定量添加した後に（ｂ）を滴下するか、または（ａ）と（ｂ）とを同時に滴下して懸濁液中の薄片状粉末表面に硫酸バリウム粒子を被覆し、
更に、
（ｃ）水溶性亜鉛化合物、及び
（ｄ）塩基性溶液、を用いて、
予め（ｃ）の所定量を添加した後に（ｄ）を滴下するか、または（ｃ）と（ｄ）とを同時に滴下して亜鉛の水化物ないし炭酸塩を被覆せしめた後、濾取し、洗浄し、乾燥し、ついで焼成することを特徴とする紫外線遮蔽用顔料の製造方法を提供するものである。
【０００９】
さらに、本発明は、上記紫外線遮蔽用顔料の所定量を含有せしめた化粧料、塗料およびプラスチックを提供するものである。
【００１０】
上記本発明に係る薄片状粒子表面に特定の粒子径を有する硫酸バリウム粒子と針状晶の酸化亜鉛粒子とが被覆された紫外線遮蔽用顔料は、高い紫外線遮蔽特性、特にＵＶ−Ａを遮蔽し、また化粧料用として用いた場合、化粧料が具備すべき伸展性、付着性のほか、色くすみが少ないという優れた特性を有している。
以下、本発明を詳細に説明する。
【００１１】
本発明で使用される薄片状粉末としては、粒子径が０．５〜１００μのマイカ、セリサイト、タルク、カオリンなどが挙げられるが、通常マイカ（白雲母）が用いられる。この薄片状粉末５〜２０重量部を、水１００重量部に懸濁させ、懸濁液を調製する。この懸濁液を５０℃以上、好ましくは、約６０〜８０℃に撹拌下昇温し、次に、以下に示す、Ａ：硫酸バリウム粒子の被覆工程及びＢ：酸化亜鉛の被覆工程に付される。
Ａ：硫酸バリウム粒子の被覆工程
懸濁液中の薄片状粉末に硫酸バリウム粒子を被覆する方法としては次の（１）または（２）の何れかの方法を採ることができる。
（１）約６０〜８０℃に昇温した懸濁液に、撹拌下、予め所定量の水溶性バリウム化合物（ａ）を添加して懸濁液中で溶解させて、その後、更に別に調製した硫酸イオンを含む溶液（ｂ）を滴下する方法。
（２）また、約６０〜８０℃に昇温した懸濁液に、撹拌下、予め所定量の水溶性バリウム化合物（ａ）の水溶液（ａ−１）を調製し、この（ａ−１）と上記（ｂ）溶液を用いて同時滴下する方法。
上記（ａ）及び（ａ−１）の水溶性バリウム化合物としては、その塩化物、硝酸塩、水酸化物等が挙げられる。また（ｂ）の硫酸イオン源としては、硫酸、硫酸ナトリウム、硫酸カリウムなどが挙げられ、その量は（ａ）のバリウムイオンの当量比より多い量が使用される。
【００１２】
Ｂ：酸化亜鉛粒子の被覆工程
酸化亜鉛粒子を被覆する工程においても、次の（１）及び（２）の何れかの方法を採ることができる。
（１）上記Ａ工程で得られた懸濁液に、予め所定量の水溶性亜鉛化合物（ｃ）を添加して溶解させ、その後、更に別に調製した塩基性溶液（ｄ）を滴下し、最終ｐＨを７以上、好ましくは８以上とする方法。
（２）また、上記Ａ工程で得られた懸濁液に、予め所定の量の水溶性亜鉛化合物（ｃ）の水溶液（ｃ−１）を調製し、この（ｃ−１）と（ｄ）とをｐＨを７以上に保ちながら同時滴下する方法。
（１）または（２）の方法によって得られた硫酸バリウム粒子と亜鉛水化物もしくは亜鉛の塩基性炭酸塩で被覆された薄片状粉末の懸濁液から、常法に従い、固形分を濾別し、洗浄、乾燥した後、焼成して所望の硫酸バリウム粒子及び酸化亜鉛粒子で被覆された顔料を得る。この焼成温度は５００〜９００℃の範囲、好ましくは６００〜８００℃の範囲で行う。５００℃未満では亜鉛が完全には酸化されない状態で残ったり、また酸化速度が遅く効率的でない。９００℃を越えると薄片状粉末表面に被覆した粒子が焼結を起こし、所期の粒子径よりも大きくなり、更には凝結を起こすようになり好ましくない。
（ｃ）及び（ｃ−１）の水溶性亜鉛化合物としては、その塩化物、硫酸塩、酢酸塩等が挙げられる。また（ｄ）の塩基性物質としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、および炭酸水素カリウムなどが挙げられる。
【００１３】
上記Ａ工程およびＢ工程における、それぞれにおいて（１）の方法、または（２）の方法の何れを選択するかは、目的とする被覆粒子の大きさによって適宜選択することが出来る。例えば、大きな被覆粒子を目指す場合は（２）の方法（以下、同時滴下法という。）が適しており、微粒子の被覆を目指す場合は（１）の方法が適している。硫酸バリウム粒子及び酸化亜鉛粒子の粒子の大きさを左右する因子としては、上記被覆方法の相違に原因する他に、懸濁液の温度、反応槽の形状、攪拌翼形状、攪拌速度等も影響する。温度を低めに設定したり、攪拌翼の回転数を高くしたり、反応槽にバッフルを設けたり、あるいは滴下速度を上げたりするなど、いずれの条件によっても、粒子径が小さくなる傾向を示す。したがって、これらの条件も目的とする粒子径となるように、適宜設定することが好ましい。また、当然のことながら、Ａ工程における（１）の方法とＢ工程における（２）の方法を組み合わせ、あるいはＡ工程における（２）の方法とＢ工程における（１）の方法を組み合わせることも任意である。
【００１４】
被覆粒子中の硫酸バリウム粒子は、酸化亜鉛粒子の凝集を防止する作用を奏するほか、特に化粧料として重要な特性である皮膚への付着性・伸展性に効果を発揮する。また酸化亜鉛粒子は、紫外線遮蔽、特に優れたＵＶ−Ａ遮蔽効果を有する物質であり、この優れた効果をさらに高め、あるいは低下せしめないようにするためには、硫酸バリウム粒子の平均粒子径を０．１〜２．０μの範囲に調製する。平均粒子径が０．１μ以下では肌に対する伸展性が低下することになり、反対に平均粒子径が２．０μ以上になると透明性が低下する原因となる。他方、酸化亜鉛粒子は、針状晶を示し、その長径の平均径が０．０５〜１．５μの結晶のものが好ましい。０．０５μ以下では、やはり肌に対する伸展性が劣ることになり、反対に１．５μ以上では紫外線遮蔽効果が低下する。
【００１５】
硫酸バリウム粒子の被覆量は、酸化亜鉛粒子の凝集性を低下せしめ、かつ化粧料に使用する場合の皮膚上の付着性・伸展性に効果を発揮するに足る必要最低限の量であればよく、薄片状粉末１００重量部に対し１０〜５０重量部が好ましい。１０重量部より少ないと、この皮膚上での伸展性が現れず、また５０重量部より多くしても伸展性の著しい向上には寄与しない。
一方、酸化亜鉛粒子は、ＵＶ−Ａの遮蔽効果を発揮するためのものであって、その為には酸化亜鉛の量を最大限増すことが好ましい。従って酸化亜鉛粒子の被覆量は、少なくとも硫酸バリウム粒子の量よりも多い量が用いられ、薄片状粉末１００重量部に対し５０〜２００重量部が好ましい範囲である。５０重量部未満では、ＵＶ−Ａの遮蔽効果が見られず、また２００重量部より増すと被覆粒子同士が薄片状粉末表面上で凝集して所望の被覆粒子の大きさにならなかったり、その被覆された粒子を介して薄片状粉末同志が凝集したり、更には薄片状粉末表面の化学的性質によっては、被覆されなくなる。
【００１６】
薄片状粉末に対する硫酸バリウムと酸化亜鉛の合わせた被覆量は、上記の範囲の量より多くすると、凝集更に粒子間の凝結が進み、解砕などの処理を行っても一次粒子が得られなくなる。
このようにして薄片状粉末表面に平均粒子径０．１〜２．０μの硫酸バリウム粒子、および針状晶の長径の平均径が０．０５〜１．５μの酸化亜鉛粒子が被覆された紫外線遮蔽用顔料が得られる。
以上述べたように、本発明に係る紫外線遮蔽用顔料は、化粧料、塗料、プラスチックに混合し優れた紫外線遮蔽効果を発揮する。特に化粧料として要求されるＵＶ−Ａ遮蔽に効果があり、しかも肌に対する伸展性・付着性が良好で、他の体質顔料、例えばタルクやマイカとオイルとの混合時の色くすみが少なく、ファンデーション用に好適な紫外線遮蔽用顔料である。
次に、実施例及び比較例を掲げて、本発明をさらに詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。
【００１７】
【実施例】
実施例１
直径１〜１５μの白雲母微粉末１５０ｇを水１．５リットルに懸濁させ、約８０℃に昇温し、攪拌下に水酸化バリウム５０．７ｇを添加する。その後、この懸濁液に攪拌下で、１０重量％の濃度の硫酸水溶液を２ｍｌ／分で滴下し、ｐＨを最終的に３とする。滴下終了後、約１０分間攪拌し、硫酸亜鉛６６２．５ｇを添加し、更に約１０分間攪拌後、３２重量％の水酸化ナトリウム水溶液を５ｍｌ／分で滴下し、最終ｐＨを８．５とする。当懸濁液から、固形分を濾別し、洗浄したのち、約１０５℃で１５時間乾燥し、更に７００℃で焼成した。このようにして白雲母微粉末１００重量部に対して硫酸バリウム粒子２５重量部および酸化亜鉛粒子１２５重量部の割合で被覆された紫外線遮蔽用顔料を得た。ＳＥＭ観察による硫酸バリウム粒子の平均径は約０．３μ、針状晶酸化亜鉛粒子の長径の平均径は約０．２μであった。
得られた紫外線遮蔽用顔料は、肌に対して伸展性、付着性が良好で、オイルと混合したときの色くすみが少なかった。
【００１８】
実施例２
直径１〜１５μの白雲母微粉末１５０ｇを水１．５リットルに懸濁させ、約８０℃に昇温し、攪拌下１０重量％の水酸化バリウム水溶液５０７ｇを加えて懸濁液中のｐＨを８．５にし、これに３０重量％濃度の硫酸水溶液を流速７．５ｍｌ／分で滴下する。その後、３０分間攪拌し、さらに攪拌下、３０重量％濃度の硫酸亜鉛水溶液２２０８ｇ及び３２重量％濃度の水酸化ナトリウム水溶液をｐＨ８．５に保ちながら、流速７．５ｍｌ／分で滴下する。滴下終了後、１０分間攪拌し、当該懸濁液から、固形分を濾別し、洗浄した後、約１０５℃で１５時間乾燥し、更に７００℃で焼成した。このようにして白雲母１００重量部に対して硫酸バリウム粒子２５重量部及び酸化亜鉛粒子１２５重量部の割合で被覆された紫外線遮蔽用顔料を得た。ＳＥＭ観察による硫酸バリウム粒子の平均径は約１．５μ、針状晶酸化亜鉛粒子の長径の平均は約０．８μであった。
得られた紫外線遮蔽用顔料は、肌に対して伸展性、付着性が良好で、オイルと混合したときの色くすみが少なかった。
【００１９】
【比較例】
比較例１
直径１〜１５μの白雲母微粉末１５０ｇを水１．５リットルに懸濁させ、約８０℃に昇温し、攪拌下に硫酸亜鉛５３０ｇを添加する。その懸濁液に３２重量％濃度の水酸化ナトリウム水溶液を５ｍｌ／分の流速で滴下し、懸濁液のｐＨを８．５とする。滴下終了後、１時間攪拌し、その懸濁液から、固形分を濾別し、洗浄した後、約１０５℃で１５時間乾燥し、更に７００℃で焼成した。
このようにして白雲母１００重量部に対して酸化亜鉛粒子１００重量部が被覆された顔料を得た。ＳＥＭ観察による針状晶の酸化亜鉛粒子の長径の平均径は、約０．２μであった。
得られた顔料の肌に対する伸展性、付着性は実施例１の顔料より劣り、紫外線遮蔽効果も実施例１、２よりも劣っていた。
【００２０】
比較例２
白雲母１００重量部に対して硫酸バリウム、４０．６重量部、および酸化亜鉛、１５重量部を被覆した顔料（特公平２−４２３８８号公報の実施例６）。
この顔料は、紫外線遮蔽効果が実施例１及び２の顔料よりも劣っていた。また、色くすみも実施例１より劣っていた。
【００２１】
［紫外線遮蔽性の性能評価］
評価試料の調製：実施例１、２及び比較例１、２記載の各顔料０．３ｇを９．７ｇの塩化ビニル樹脂系メジウムインキに添加、分散混合し、得られた分散体を厚さ１２０μｍのアプリケーターを用いてガラスプレート上に塗布し、乾燥させ、評価試料とした。
紫外線透過率の測定法：上記各評価試料を分光光度計（２２８型、日立社製）を用いて波長２００〜７００ｎｍ範囲の透過率を測定した（図１参照）。縦軸は透過率（％）を、横軸は波長（ｎｍ）を示す。この結果、実施例１、２で得られた粉体は、比較例１、２に比べて、測定した紫外波長領域（４００ｎｍ以下）およびＵＶ−Ａ領域での透過率が小さく、しかもＵＶ−Ａ領域において、吸収と見られる透過率の極小点が現れ、従って良好な紫外線遮蔽効果が認められた。
【００２２】
［色くすみ度の評価］
実施例及び比較例で調製された各顔料と流動パラフィンとをそれぞれ混合し、混合前の含量粉体の色相と混合後の色相の差を比較し、化粧料調製時に重要な因子である色くすみ度をカラーメター（ＣＲ−３００：ミノルタ製）で測定した。その結果を図２に示す。図中、縦軸△Ｅ*は色差であり、Ｌ値（明度）、ａ値（赤、緑の指標）及びｂ値（黄色、青の指標）から、下記の式により算出した。また、横軸は流動パラフィンの含有量（％）である。
【数１】

Figure 0003848742
この結果、実施例１の顔料は、比較例２及び雲母体質顔料と比較して色くすみが少なく、化粧料用顔料として適していることが確認された。
【００２３】
次に、実施例、比較例で調製された各顔料及びマイカについて、亜麻仁油を用いて吸油量を調べた。その結果を表１に示す。この結果、実施例１及び実施例２の顔料は、硫酸バリウムが被覆されていない比較例１の顔料より吸油量が少なく、コンパクトパウダー等の化粧料を調製した際のケーキの成型性に良好な効果を有することが確認された。
【００２４】
【表１】
表１：顔料の吸油量
顔料 吸油量（ｍｌ／１００ｇ）
実施例１ ８１
実施例２ ５５
比較例１ ９７
比較例２ ６５
Ｍｉｃａ−Ｍ * ５３
＊：Ｍｅｒｃｋ社製雲母体質顔料
【００２５】
以下に本発明の紫外線遮蔽用顔料を用いた使用例を示す。
【使用例】
使用例１（コンパクトパウダー）
組成
実施例１又は２で得られた紫外線遮蔽用顔料 ２５重量部
着色顔料 ５重量部
ラノリン ３重量部
ミリスチン酸イソプロピル バランス
ステアリン酸マグネシウム ２重量部
タルク ５０重量部
【００２６】
使用例２（自動車用塗料）
組成
組成Ａ（アクリルメラミン樹脂）：
アクリディック４７−７１２ ７０重量部
スーパーベッカミンＧ８２１−６０ ３０重量部
組成Ｂ：
実施例１又は２で得られた紫外線遮蔽用顔料 １０重量部
パール顔料 １０重量部
組成Ｃ（アクリルメラミン樹脂用シンナー）；
酢酸エチル ５０重量部
トルエン ３０重量部
ｎ−ブタノール １０重量部
ソルベッソ＃１５０ ４０重量部
組成Ａと組成Ｂとを混合した物をスプレー塗装に適した粘度（フォードカップ＃４で１２〜１５秒）に組成Ｃを用いて稀釈し、スプレー塗装にてベースコート層を形成する。
【００２７】
使用例３（プラスチック組成物）
組成
高密度ポリエチレン樹脂（ペレット） １００重量部
実施例１又は２で得られた紫外線遮蔽用顔料 １重量部
マグネシウムステアレート ０．１重量部
ジンクステアレート ０．１重量部
上記配合比によるペレットをドライブレンドし射出成型を行う。
【図面の簡単な説明】
【図１】 実施例１及び２と、比較例１及び２の各顔料の紫外光波長領域２００〜７００ｎｍにおける透過率を示す図である。
【図２】 実施例１及び２と、比較例１及び２の各顔料の色くすみ度を調べた結果のグラフである。[0001]
[Industrial application fields]
The present invention relates to an ultraviolet shielding pigment, and more particularly to an ultraviolet shielding pigment in which zinc oxide particles and barium sulfate particles are coated on the surface of a flaky powder, in particular, to shield UV-A, a production method thereof, and a use thereof.
[0002]
[Background]
The amount of light on the ground with a wavelength of 290 to 400 nm in the ultraviolet region occupies about 6% of the sunlight, and the 290 to 320 nm region on the short wavelength side (hereinafter referred to as UV-B) is about 0.5. %, 320 to 400 nm (hereinafter referred to as UV-A) on the long wavelength side is about 5.5%, and the amount of UV-A light is large. Since this UV-A has a long wavelength, it is more likely to pass through clouds and window glass than ultraviolet rays having a short wavelength, and the amount of skin exposure in daily life increases, and further reaches the deep part of the skin tissue. UV-B is scattered or absorbed in the epidermis and causes inflammation such as sunburn in the skin, whereas UV-A penetrates into the subcutaneous dermis, radicals are generated inside the skin tissue, wrinkles, It is said to cause photoaging such as loosening and reduced elasticity, and to adversely affect cell membranes and genes. Therefore, in order to prevent ultraviolet rays, it is important not only to shield the entire ultraviolet region but also to shield this UV-A, and the interest is increasing (Cosmetics Journal 31 No. 1). p.14-30 1997).
[0003]
Examples of the material having an ultraviolet shielding effect include fine particle titanium oxide (for example, Japanese Patent Publication No. 47-42502), fine particle iron oxide (for example, Japanese Patent Application Laid-Open No. 5-279235), and fine particle zinc oxide (for example, Japanese Patent Application Laid-Open No. 60-60). -231607) and metal oxides such as fine particle cerium oxide (for example, JP-A-2-82312), benzotriazole-based organic ultraviolet absorbers, and the like are known and commercially available. However, these commercially available ultraviolet shielding agents or absorbents have the following problems to be improved, such as an insufficient ultraviolet shielding effect or a limited purpose of use.
[0004]
For example, fine particle titanium oxide has a small absorption of UV-A, and in order to exert a shielding effect by light scattering in the UV-A region, its particle diameter must be increased. Loss of properties and whiteness increase, resulting in limited use. Fine particle iron oxide is inferior in ultraviolet shielding effect compared with other metal oxides, and itself has a brown color, so that its application is limited. Fine zinc oxide has an excellent ultraviolet shielding effect, but has a strong cohesiveness and a special dispersing device with a strong stirring force to disperse into primary particles with a particle size that provides an optimum ultraviolet shielding effect. However, once the primary particles can be dispersed, there is a problem in use that they easily reaggregate.
[0005]
In addition, fine cerium oxide is extremely expensive, so it can be said that there is almost no practical use except for a special purpose.
On the other hand, organic ultraviolet absorbers such as benzotriazole are excellent in ultraviolet absorptivity but are basically lacking in stability because they are organic compounds, and it is not possible to expect sustained effects. In addition, the use of organic ultraviolet absorbers as cosmetic additives is severely imposed and restricted from the viewpoint of safety.
[0006]
In light of the above circumstances, the present inventors have made extensive research on ultraviolet shielding pigments, and as a result, by coating zinc oxide particles and barium sulfate particles on flaky powder, a high ultraviolet shielding effect, In particular, it has been found that UV-A is shielded and the cohesiveness of zinc oxide is improved, and when added to cosmetics, an ultraviolet shielding pigment having excellent basic properties, extensibility and adhesion. Successfully developed. The present invention is based on such knowledge.
[0007]
DISCLOSURE OF THE INVENTION
The present invention is characterized in that the surface of a flaky powder is coated with barium sulfate particles having an average particle diameter of 0.1 to 2.0 μm and zinc oxide needle crystal particles having an average long diameter of 0.05 to 1.5 μm. An ultraviolet shielding pigment is provided.
[0008]
In the present invention, the flaky powder is suspended in water, and the suspension contains (a) a water-soluble barium compound, and (b) a solution containing sulfate ions greater than the equivalent ratio of the barium ions in (a). Using,
(B) is dropped after a predetermined amount of (a) is added in advance, or (a) and (b) are dropped simultaneously to coat the surface of the flaky powder in the suspension with barium sulfate particles,
Furthermore,
Using (c) a water-soluble zinc compound and (d) a basic solution,
(D) is added dropwise after a predetermined amount of (c) has been added in advance, or (c) and (d) are simultaneously added dropwise to coat a zinc hydrate or carbonate, and then filtered. An object of the present invention is to provide a method for producing an ultraviolet shielding pigment, which is washed, dried and then fired.
[0009]
Furthermore, the present invention provides cosmetics, paints and plastics containing a predetermined amount of the above-mentioned ultraviolet shielding pigment.
[0010]
The ultraviolet shielding pigment in which the surface of the flaky particle according to the present invention is coated with barium sulfate particles having a specific particle diameter and acicular zinc oxide particles has high ultraviolet shielding properties, in particular, UV-A shielding. In addition, when used for cosmetics, in addition to extensibility and adhesion that the cosmetics should have, it has excellent properties such as less color dullness.
Hereinafter, the present invention will be described in detail.
[0011]
Examples of the flaky powder used in the present invention include mica, sericite, talc, kaolin and the like having a particle size of 0.5 to 100 μm, and usually mica (muscovite) is used. A suspension is prepared by suspending 5 to 20 parts by weight of the flaky powder in 100 parts by weight of water. The suspension is heated to 50 ° C. or higher, preferably about 60 to 80 ° C. with stirring, and then subjected to A: a barium sulfate particle coating step and B: zinc oxide coating step, as shown below. The
A: Barium sulfate particle coating step As a method of coating the flaky powder in the suspension with the barium sulfate particles, either of the following methods (1) or (2) may be employed.
(1) A predetermined amount of a water-soluble barium compound (a) was added in advance to a suspension heated to about 60 to 80 ° C. with stirring, and dissolved in the suspension. A method of dropping the solution (b) containing sulfate ions.
(2) A predetermined amount of an aqueous solution (a-1) of a water-soluble barium compound (a) is prepared in advance in a suspension heated to about 60 to 80 ° C. with stirring, and this (a-1) And (b) a method of simultaneously dripping using the solution.
Examples of the water-soluble barium compounds (a) and (a-1) include chlorides, nitrates and hydroxides thereof. Examples of the sulfate ion source in (b) include sulfuric acid, sodium sulfate, potassium sulfate, and the like, and the amount thereof is larger than the equivalent ratio of barium ions in (a).
[0012]
B: Zinc oxide particle coating step In the step of coating zinc oxide particles, any one of the following methods (1) and (2) can be employed.
(1) A predetermined amount of a water-soluble zinc compound (c) is added in advance to the suspension obtained in the above step A and dissolved, and then a separately prepared basic solution (d) is added dropwise. A method of adjusting the pH to 7 or more, preferably 8 or more.
(2) Also, a predetermined amount of an aqueous solution (c-1) of a water-soluble zinc compound (c) is prepared in advance in the suspension obtained in the above step A, and (c-1) and (d) And simultaneously dropping while maintaining the pH at 7 or higher.
From the suspension of flaky powder coated with barium sulfate particles and zinc hydrate or zinc basic carbonate obtained by the method of (1) or (2), the solid content is separated by filtration according to a conventional method. After washing, drying, and firing, a pigment coated with desired barium sulfate particles and zinc oxide particles is obtained. The firing temperature is in the range of 500 to 900 ° C, preferably in the range of 600 to 800 ° C. Below 500 ° C., zinc remains in a state where it is not completely oxidized, and the oxidation rate is slow and not efficient. If the temperature exceeds 900 ° C., the particles coated on the surface of the flaky powder cause sintering, become larger than the intended particle diameter, and further cause aggregation, which is not preferable.
Examples of the water-soluble zinc compounds (c) and (c-1) include chlorides, sulfates and acetates thereof. Examples of the basic substance (d) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
[0013]
Which of the method (1) and the method (2) is selected in each of the steps A and B can be appropriately selected depending on the size of the target coated particles. For example, the method (2) (hereinafter referred to as the simultaneous dropping method) is suitable when aiming at large coated particles, and the method (1) is suitable when aiming at coating fine particles. Factors that influence the size of the barium sulfate particles and zinc oxide particles are caused by the difference in the coating method, as well as the temperature of the suspension, the shape of the reaction vessel, the shape of the stirring blade, the stirring speed, etc. To do. The particle diameter tends to be small depending on any conditions such as setting the temperature low, increasing the rotation speed of the stirring blade, providing a baffle in the reaction tank, or increasing the dropping speed. Therefore, it is preferable to appropriately set these conditions so that the target particle size is obtained. Of course, the method (1) in the step A and the method (2) in the step B may be combined, or the method (2) in the step A and the method (1) in the step B may be combined arbitrarily. It is.
[0014]
The barium sulfate particles in the coated particles have the effect of preventing aggregation of the zinc oxide particles, and are particularly effective in adhesion and extensibility to the skin, which is an important characteristic for cosmetics. Zinc oxide particles are a substance having an ultraviolet shielding property, particularly an excellent UV-A shielding effect. In order to further enhance or prevent this superior effect, the average particle diameter of the barium sulfate particles is reduced. Prepare in the range of 0.1-2.0μ. When the average particle size is 0.1 μm or less, the extensibility to the skin is lowered, and conversely, when the average particle size is 2.0 μm or more, the transparency is lowered. On the other hand, the zinc oxide particles show needle-like crystals, and those having an average major axis diameter of 0.05 to 1.5 μm are preferable. If it is 0.05 μm or less, the extensibility to the skin is also inferior, whereas if it is 1.5 μm or more, the ultraviolet shielding effect is lowered.
[0015]
The coating amount of barium sulfate particles may be the minimum amount necessary to reduce the cohesiveness of zinc oxide particles and to exert an effect on adhesion and extensibility on the skin when used in cosmetics. The amount is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the flaky powder. If the amount is less than 10 parts by weight, the extensibility on the skin does not appear, and if the amount exceeds 50 parts by weight, the extensibility is not significantly improved.
On the other hand, the zinc oxide particles are for exhibiting a UV-A shielding effect, and for this purpose, it is preferable to increase the amount of zinc oxide to the maximum. Accordingly, the coating amount of the zinc oxide particles is at least larger than the amount of the barium sulfate particles, and is preferably 50 to 200 parts by weight with respect to 100 parts by weight of the flaky powder. If the amount is less than 50 parts by weight, the UV-A shielding effect is not observed, and if the amount is more than 200 parts by weight, the coated particles are not aggregated on the surface of the flaky powder to obtain the desired coated particle size. The flaky powders agglomerate through the coated particles, and further, depending on the chemical properties of the flaky powder surface, they are not coated.
[0016]
If the total coating amount of barium sulfate and zinc oxide on the flaky powder is larger than the above range, aggregation further progresses between the particles, and primary particles cannot be obtained even if processing such as pulverization is performed.
The ultraviolet rays in which the surface of the flaky powder was coated with the barium sulfate particles having an average particle diameter of 0.1 to 2.0 μm and the zinc oxide particles having an average diameter of acicular crystals of 0.05 to 1.5 μm were coated. A shielding pigment is obtained.
As described above, the ultraviolet shielding pigment according to the present invention exhibits an excellent ultraviolet shielding effect when mixed with cosmetics, paints and plastics. Particularly effective for UV-A shielding required for cosmetics, has good extensibility and adhesion to the skin, has little color dullness when mixed with other extender pigments such as talc, mica and oil, and foundation It is an ultraviolet shielding pigment suitable for use.
EXAMPLES Next, although an Example and a comparative example are hung up and this invention is demonstrated further in detail, this invention is not limited by these Examples.
[0017]
【Example】
Example 1
150 g of fine muscovite powder having a diameter of 1 to 15 μ is suspended in 1.5 liters of water, heated to about 80 ° C., and 50.7 g of barium hydroxide is added with stirring. Thereafter, an aqueous sulfuric acid solution having a concentration of 10% by weight is added dropwise to the suspension at a rate of 2 ml / min, and the pH is finally set to 3. After completion of the dropping, the mixture is stirred for about 10 minutes, 662.5 g of zinc sulfate is added, and further stirred for about 10 minutes, and then a 32 wt% aqueous sodium hydroxide solution is added dropwise at 5 ml / min to a final pH of 8.5. . Solids were filtered off from the suspension, washed, dried at about 105 ° C. for 15 hours, and calcined at 700 ° C. In this way, an ultraviolet shielding pigment coated at a ratio of 25 parts by weight of barium sulfate particles and 125 parts by weight of zinc oxide particles to 100 parts by weight of fine muscovite powder was obtained. According to SEM observation, the average diameter of the barium sulfate particles was about 0.3 μm, and the longest average diameter of the acicular zinc oxide particles was about 0.2 μm.
The obtained ultraviolet shielding pigment had good extensibility and adhesion to the skin, and had less color dullness when mixed with oil.
[0018]
Example 2
Suspend 150 g of muscovite fine powder with a diameter of 1 to 15 μ in 1.5 liters of water, raise the temperature to about 80 ° C., and add 507 g of a 10 wt% barium hydroxide aqueous solution with stirring to adjust the pH in the suspension. To 8.5, a 30% by weight aqueous sulfuric acid solution is added dropwise at a flow rate of 7.5 ml / min. Thereafter, the mixture is stirred for 30 minutes, and further, 2208 g of a 30 wt% aqueous zinc sulfate solution and a 32 wt% aqueous sodium hydroxide solution are added dropwise at a flow rate of 7.5 ml / min with stirring. After completion of the dropwise addition, the mixture was stirred for 10 minutes, and the solid content was separated from the suspension by filtration, washed, dried at about 105 ° C. for 15 hours, and further calcined at 700 ° C. In this manner, an ultraviolet shielding pigment coated with 25 parts by weight of barium sulfate particles and 125 parts by weight of zinc oxide particles with respect to 100 parts by weight of muscovite was obtained. According to SEM observation, the average diameter of the barium sulfate particles was about 1.5 μm, and the average long diameter of the acicular zinc oxide particles was about 0.8 μm.
The obtained ultraviolet shielding pigment had good extensibility and adhesion to the skin, and had less color dullness when mixed with oil.
[0019]
[Comparative example]
Comparative Example 1
150 g of fine muscovite powder having a diameter of 1 to 15 μ is suspended in 1.5 liters of water, heated to about 80 ° C., and 530 g of zinc sulfate is added with stirring. A 32% strength by weight aqueous sodium hydroxide solution is added dropwise to the suspension at a flow rate of 5 ml / min to adjust the pH of the suspension to 8.5. After completion of the dropping, the mixture was stirred for 1 hour, and the solid content was separated from the suspension by filtration, washed, dried at about 105 ° C. for 15 hours, and further calcined at 700 ° C.
Thus, a pigment coated with 100 parts by weight of zinc oxide particles with respect to 100 parts by weight of muscovite was obtained. The average diameter of the major axis of the acicular zinc oxide particles observed by SEM was about 0.2 μm.
The extensibility and adhesion of the obtained pigment to the skin were inferior to the pigment of Example 1, and the ultraviolet shielding effect was also inferior to Examples 1 and 2.
[0020]
Comparative Example 2
A pigment in which barium sulfate, 40.6 parts by weight, and zinc oxide, 15 parts by weight are coated on 100 parts by weight of muscovite (Example 6 of JP-B-2-42388).
This pigment was inferior to the pigments of Examples 1 and 2 in the ultraviolet shielding effect. Moreover, the color dullness was also inferior to Example 1.
[0021]
[Evaluation of UV shielding performance]
Preparation of evaluation sample: 0.3 g of each pigment described in Examples 1 and 2 and Comparative Examples 1 and 2 was added to 9.7 g of vinyl chloride resin-based medium ink, dispersed and mixed, and the resulting dispersion was 120 μm thick. An applicator was applied on a glass plate and dried to obtain an evaluation sample.
Method for measuring ultraviolet transmittance: Transmittance in the wavelength range of 200 to 700 nm was measured for each of the above-described evaluation samples using a spectrophotometer (type 228, manufactured by Hitachi) (see FIG. 1). The vertical axis represents transmittance (%), and the horizontal axis represents wavelength (nm). As a result, the powders obtained in Examples 1 and 2 have a lower transmittance in the measured ultraviolet wavelength region (400 nm or less) and UV-A region than in Comparative Examples 1 and 2, and UV-A. In the region, a minimum point of transmittance, which appears to be absorption, appeared, and thus a good ultraviolet shielding effect was observed.
[0022]
[Evaluation of color dullness]
Each pigment prepared in Examples and Comparative Examples is mixed with liquid paraffin, and the difference between the hue of the powder before mixing and the hue after mixing is compared. Color dullness, which is an important factor when preparing cosmetics, is used. The degree was measured with a color meter (CR-300: manufactured by Minolta). The result is shown in FIG. In the figure, the vertical axis ΔE * is a color difference, and was calculated from the L value (lightness), a value (red and green indexes) and b value (yellow and blue indexes) by the following formula. The horizontal axis represents the content (%) of liquid paraffin.
[Expression 1]
Figure 0003848742
As a result, it was confirmed that the pigment of Example 1 had less color dullness than Comparative Example 2 and the mica extender pigment, and was suitable as a cosmetic pigment.
[0023]
Next, the oil absorption amount of each pigment and mica prepared in Examples and Comparative Examples was examined using linseed oil. The results are shown in Table 1. As a result, the pigments of Example 1 and Example 2 have less oil absorption than the pigment of Comparative Example 1 that is not coated with barium sulfate, and are excellent in cake moldability when a cosmetic such as compact powder is prepared. It was confirmed to have an effect.
[0024]
[Table 1]
Table 1: Oil absorption of pigment
Pigment oil absorption (ml / 100g)
Example 1 81
Example 2 55
Comparative Example 1 97
Comparative Example 2 65
Mica-M * 53
*: Mica body pigment manufactured by Merck [0025]
Examples of use using the ultraviolet shielding pigment of the present invention are shown below.
【Example of use】
Use example 1 (compact powder)
UV shielding pigment obtained in Composition Example 1 or 2 25 parts by weight Colored pigment 5 parts by weight Lanolin 3 parts by weight Isopropyl myristate Balance magnesium stearate 2 parts by weight Talc 50 parts by weight
Use Example 2 (Automobile paint)
Composition A (acryl melamine resin):
Acridic 47-712 70 parts by weight Superbecamine G821-60 30 parts by weight Composition B:
UV shielding pigment obtained in Example 1 or 2 10 parts by weight pearl pigment 10 parts by weight composition C (a thinner for acrylic melamine resin);
Ethyl acetate 50 parts by weight Toluene 30 parts by weight n-Butanol 10 parts by weight Solvesso # 150 40 parts by weight A mixture of composition A and composition B has a viscosity suitable for spray coating (12-15 seconds with Ford Cup # 4) Dilute with Composition C and form base coat layer by spray coating.
[0027]
Use Example 3 (Plastic composition)
Composition High-density polyethylene resin (pellet) 100 parts by weight UV shielding pigment obtained in Example 1 or 2 1 part by weight Magnesium stearate 0.1 part by weight zinc stearate 0.1 part by weight Blend and perform injection molding.
[Brief description of the drawings]
FIG. 1 is a graph showing the transmittance in the ultraviolet wavelength region of 200 to 700 nm of pigments of Examples 1 and 2 and Comparative Examples 1 and 2. FIG.
FIG. 2 is a graph showing the result of examining the color dullness of the pigments of Examples 1 and 2 and Comparative Examples 1 and 2.

Claims (4)

薄片状粉末表面に平均粒子径０．１〜２．０μの硫酸バリウム粒子および長径の平均径が０．０５〜１．５μの酸化亜鉛針状晶粒子を被覆せしめたことを特徴とする紫外線遮蔽用顔料。UV shielding characterized in that the surface of flaky powder is coated with barium sulfate particles having an average particle diameter of 0.1 to 2.0 μm and zinc oxide needle crystal particles having an average diameter of 0.05 to 1.5 μm. Pigments. 上記硫酸バリウムの量が酸化亜鉛の量より少ない量であって、薄片状粉末１００重量部に対し硫酸バリウムが１０〜５０重量部、酸化亜鉛が５０〜２００重量部の量比である請求項１記載の紫外線遮蔽用顔料。The amount of the barium sulfate is less than the amount of zinc oxide, and the ratio is 10 to 50 parts by weight of barium sulfate and 50 to 200 parts by weight of zinc oxide with respect to 100 parts by weight of the flaky powder. The ultraviolet shielding pigment as described. 薄片状粉末を水に懸濁させ、この懸濁液に
（ａ）水溶性バリウム化合物、及び
（ｂ）（ａ）のバリウムイオンの当量比より多い硫酸イオンを含む溶液、を用いて、
予め（ａ）の所定量を添加した後に（ｂ）を滴下するか、または（ａ）と（ｂ）とを同時に滴下して懸濁液中の薄片状粉末表面に硫酸バリウム粒子を被覆し、
更に、
（ｃ）水溶性亜鉛化合物、及び
（ｄ）塩基性溶液を用いて、
予め（ｃ）の所定量を添加した後に（ｄ）を滴下するか、または（ｃ）と（ｄ）とを同時に滴下して亜鉛の水化物ないし炭酸塩を被覆せしめた後、濾取し、洗浄し、乾燥し、次いで焼成することを特徴とする請求項１または請求項２記載の紫外線遮蔽用顔料の製造方法。The flaky powder is suspended in water, and the suspension contains (a) a water-soluble barium compound and (b) a solution containing sulfate ions greater than the equivalent ratio of barium ions in (a).
(B) is added dropwise after a predetermined amount of (a) is added in advance, or (a) and (b) are added dropwise at the same time to coat barium sulfate particles on the surface of the flaky powder in the suspension,
Furthermore,
Using (c) a water-soluble zinc compound and (d) a basic solution,
(D) is added dropwise after adding a predetermined amount of (c) in advance, or (c) and (d) are simultaneously added dropwise to coat a zinc hydrate or carbonate, and then filtered. The method for producing an ultraviolet shielding pigment according to claim 1, wherein the pigment is washed, dried, and then fired. 請求項１または請求項２記載の紫外線遮蔽用顔料を含有せしめたことを特徴とする化粧料、塗料およびプラスチック。Cosmetics, paints, and plastics containing the ultraviolet shielding pigment according to claim 1 or 2.
JP19202197A 1997-07-03 1997-07-03 UV shielding pigment Expired - Lifetime JP3848742B2 (en)

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ES98111383T ES2207769T3 (en) 1997-07-03 1998-06-20 PIGMENT FOR PROTECTION AGAINST ULTRAVIOLET RADIATION.
DE69818556T DE69818556T2 (en) 1997-07-03 1998-06-20 Shielding pigment against ultraviolet radiation
EP98111383A EP0889099B1 (en) 1997-07-03 1998-06-20 Pigment for shielding of ultraviolet radiation
TW087110588A TW513471B (en) 1997-07-03 1998-06-30 Process for manufacturing a pigment for shielding of ultraviolet radiation
KR1019980026581A KR100538606B1 (en) 1997-07-03 1998-07-02 Pigment for shielding of ultraviolet radiation
US09/109,085 US6086666A (en) 1997-07-03 1998-07-02 Pigment for shielding of ultraviolet radiation
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